WO2011034026A1 - Composition lubrifiante et mécanisme à glissement l'utilisant - Google Patents

Composition lubrifiante et mécanisme à glissement l'utilisant Download PDF

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WO2011034026A1
WO2011034026A1 PCT/JP2010/065747 JP2010065747W WO2011034026A1 WO 2011034026 A1 WO2011034026 A1 WO 2011034026A1 JP 2010065747 W JP2010065747 W JP 2010065747W WO 2011034026 A1 WO2011034026 A1 WO 2011034026A1
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Prior art keywords
sliding
atom
lubricating oil
containing compound
carbon atoms
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PCT/JP2010/065747
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English (en)
Japanese (ja)
Inventor
杜継 葛西
山田　亮
正憲 辻岡
三宅　浩二
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出光興産株式会社
日本アイ・ティ・エフ株式会社
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Application filed by 出光興産株式会社, 日本アイ・ティ・エフ株式会社 filed Critical 出光興産株式会社
Priority to US13/395,801 priority Critical patent/US20120177915A1/en
Priority to CN2010800418421A priority patent/CN102597191A/zh
Priority to EP10817139.8A priority patent/EP2479247A4/fr
Publication of WO2011034026A1 publication Critical patent/WO2011034026A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/06—Metal salts
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/042—Metal salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/023—Multi-layer lubricant coatings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/023—Multi-layer lubricant coatings
    • C10N2050/025—Multi-layer lubricant coatings in the form of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2080/00—Special pretreatment of the material to be lubricated, e.g. phosphatising or chromatising of a metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer

Definitions

  • the present invention relates to a lubricating oil composition and a sliding mechanism using the lubricating oil composition, and more particularly, a lubricating oil composition exhibiting a very low friction coefficient when used as a lubricating oil for a low friction sliding material
  • the present invention relates to a sliding mechanism having a low coefficient of friction using the lubricating oil composition.
  • lubricants various base oils and additives have been developed so far in order to improve various performances.
  • the performance required for engine oil includes appropriate viscosity characteristics, oxidation stability, clean dispersibility, antiwear, antifogging, etc., and these performances can be improved by combining various base oils and additives. Is planned.
  • zinc dialkyldithiophosphate (ZnDTP) is often used as an engine oil additive because it is an excellent anti-wear additive.
  • the sliding material as a material for a part having a severe frictional wear environment (for example, a sliding part of an engine), there is a material having a hard film such as a TiN film or a CrN film that contributes to an improvement in wear resistance.
  • a material having a hard film such as a TiN film or a CrN film that contributes to an improvement in wear resistance.
  • the friction coefficient can be lowered by using a diamond-like carbon (DLC) film in the air and in the absence of a lubricating oil, and a material having a DLC film (hereinafter referred to as a DLC material) has a low friction sliding property.
  • a DLC material a material having a DLC film
  • Patent Document 1 discloses a lubricating oil composition used for a low friction sliding member containing an ether-based ashless friction reducing agent.
  • Patent Documents 2 and 3 include a fatty acid ester-based ashless friction modifier and an aliphatic amine-based ashless friction adjustment on the sliding surface between the DLC member and the iron base member and the sliding surface between the DLC member and the aluminum alloy member.
  • Patent Document 4 discloses a technique using a low friction agent composition containing an oxygen-containing organic compound or an aliphatic amine compound in a low friction sliding mechanism having a DLC coating sliding member.
  • Lubricating oil compositions for low-friction sliding materials have been developed in this way, but even when these technologies are applied, the friction coefficient can be increased by adding ZnDTP to further improve wear resistance. Tended to be larger. Therefore, even if ZnDTP is not used, various performances required for the lubricating oil can be maintained, and a lubricating oil composition exhibiting an extremely low friction coefficient when used as a lubricating oil for a low friction sliding material in particular. It has been demanded.
  • JP 2006-36850 A Japanese Patent Laid-Open No. 2003-238882 Japanese Patent Application Laid-Open No. 2004-155891 JP 2005-98495 A
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a lubricating oil composition exhibiting an extremely low friction coefficient when used as a lubricating oil for a low friction sliding material.
  • the present invention has a specific low friction sliding material film on the sliding surface using a lubricating oil composition that can exhibit excellent low friction properties while maintaining various characteristics as a lubricating oil.
  • An object of the present invention is to provide a sliding mechanism excellent in low friction by combining with a sliding member.
  • the inventors of the present invention can exhibit excellent low friction properties while maintaining various properties as the above-described lubricating oil by a lubricating oil composition containing a specific additive. It is found that the above-mentioned problem can be solved by configuring a sliding mechanism with a lubricating oil composed of this lubricating oil composition and a sliding member on which a DLC film formed by adding a specific component is formed. It was. The present invention has been completed based on such findings.
  • X 1 and X 2 represent an oxygen atom or a sulfur atom.
  • R 1 represents an organic group having 2 to 30 carbon atoms containing an oxygen atom or a sulfur atom.
  • N is an integer selected from 1 to 3. is there)
  • a phosphorus-zinc-containing compound obtained by reacting a phosphorus-containing compound represented by formula (II) with a zinc compound, and the general formula (II)
  • a lubricating oil composition (referred to as invention 1) used for a low friction sliding material, comprising an additive selected from sulfur-containing compounds represented by 2.
  • the additive is a phosphorus-zinc-containing compound obtained by using a phosphorus-containing compound in which at least one of X 1 and X 2 in the formula (I) is an oxygen atom , 3.
  • the additive is represented by the general formula (III)
  • R 6 and R 7 are each independently an organic group having 1 to 29 carbon atoms which may contain an atom selected from an oxygen atom, a sulfur atom and a nitrogen atom, A 3 and A 4 are Each independently represents a divalent hydrocarbon group having 1 to 12 carbon atoms
  • the lubricating oil composition according to 1 above which is a sulfur-containing compound represented by: 5.
  • the lubricating oil composition according to 1 above, wherein the low friction sliding material is a material having a diamond-like carbon (DLC) film, 6).
  • DLC diamond-like carbon
  • a sliding mechanism in which the lubricating oil composition according to the above 1 is interposed between sliding surfaces of two sliding members that slide on each other, and at least one sliding surface of the two sliding members A sliding mechanism in which a DLC film containing 5 to 50 atom% hydrogen is formed (referred to as invention 2), 7).
  • One or more metal layers selected from titanium (Ti), chromium (Cr), tungsten (W), and silicon (Si), a metal nitride layer, or a metal between the sliding member and the DLC film
  • the sliding mechanism according to the above 7 having a carbonized layer, 10.
  • the lubricating oil has the general formula (I)
  • X 1 and X 2 represent an oxygen atom or a sulfur atom.
  • R 1 represents an organic group having 2 to 30 carbon atoms containing an oxygen atom or a sulfur atom.
  • N is an integer selected from 1 to 3. is there)
  • a phosphorus-zinc-containing compound obtained by reacting a phosphorus-containing compound represented by formula (II) with a zinc compound, and the general formula (II)
  • a lubricating oil composed of a lubricating oil composition comprising an additive selected from sulfur-containing compounds represented by the formula, wherein a DLC film is formed on at least one sliding surface of two sliding members.
  • the DLC film includes 1 to 30 atom% of tungsten (W) or molybdenum (Mo), and a sliding mechanism (referred to as invention 3), 12
  • An intermediate layer is provided between the sliding member and the DLC film, and the intermediate layer is any one selected from titanium (Ti), chromium (Cr), tungsten (W), and silicon (Si).
  • the sliding mechanism according to 11 above comprising one or more of a metal metal layer, a metal nitride layer, or a metal carbide layer, wherein the total thickness of the intermediate layer is 0.1 to 2.0 ⁇ m.
  • the additive is represented by the general formula (III)
  • R 6 and R 7 are each independently an organic group having 1 to 29 carbon atoms which may contain an atom selected from an oxygen atom, a sulfur atom and a nitrogen atom, A 3 and A 4 are Each independently represents a divalent hydrocarbon group having 1 to 12 carbon atoms) 15.
  • the sliding mechanism according to 15 above which is a sulfur-containing compound represented by
  • the present invention it is possible to provide a lubricating oil composition that exhibits a very low friction coefficient when used as a lubricating oil for a low friction sliding material. Further, according to the present inventions 2 and 3, the sliding mechanisms 1 and 2 excellent in low friction are provided in the combination of the lubricating oil composition and a sliding surface coated with a specific low friction sliding material. be able to.
  • FIG. 1 It is sectional drawing which shows typically the structure of the sliding member which has the DLC film of the sliding mechanisms 1 and 2 which concern on one embodiment of this invention 2 and 3.
  • FIG. It is sectional drawing which shows typically the structure of the sliding member which has the DLC film of the sliding mechanisms 1 and 2 which concern on other embodiment of this invention 2 and 3.
  • FIG. It is a figure which shows the outline
  • FIG. It is an example of a measurement of the X-ray diffraction spectrum of the DLC film concerning one embodiment of the present invention 2 and 3. It is a differential spectrum of the DLC film of FIG. It is a figure which shows the crystal peak extraction of the DLC film of FIG.
  • the present invention relates to a lubricating oil composition (Invention 1) and a sliding mechanism (Inventions 2 and 3) using the lubricating oil composition.
  • Invention 1 a lubricating oil composition
  • Inventions 2 and 3 a sliding mechanism using the lubricating oil composition.
  • Invention 1 ⁇ Lubricating oil composition>
  • the lubricating oil composition of the present invention 1 contains a lubricating base oil and a specific additive, and is used as a lubricating oil used for a sliding surface of a low friction sliding material.
  • the lubricating base oil used by this invention can select suitably from well-known mineral base oil and synthetic base oil used conventionally.
  • the mineral oil for example, a distillate obtained by atmospheric distillation of paraffinic crude oil, intermediate crude oil or naphthenic crude oil, or vacuum distillation residual oil, or The refined oil obtained by refine
  • examples of synthetic oils include poly ⁇ -olefins, polybutenes, polybutenes, polyol esters, and alkylbenzenes, which are ⁇ -olefin oligomers having 8 to 14 carbon atoms.
  • the said mineral oil may be used 1 type as a base oil, and may be used in combination of 2 or more type.
  • the said synthetic oil may be used 1 type and may be used in combination of 2 or more type.
  • one or more mineral oils and one or more synthetic oils may be used in combination.
  • the base oil those having a kinematic viscosity at 100 ° C. of usually 2 to 50 mm 2 / s, preferably 3 to 30 mm 2 / s, particularly preferably 3 to 15 mm 2 / s are advantageous.
  • the kinematic viscosity at 100 ° C. is 2 mm 2 / s or more, the evaporation loss is small, and when it is 50 mm 2 / s or less, the power loss due to the viscous resistance is suppressed, and the fuel efficiency improvement effect is exhibited well.
  • the base oil preferably has a viscosity index of 60 or more, more preferably 70 or more, and particularly preferably 80 or more. When the viscosity index is 60 or more, the viscosity change due to the temperature of the base oil is small, and stable lubricating performance is exhibited.
  • a phosphorus-zinc-containing compound obtained by reacting a specific phosphorus-containing compound with a zinc compound or a specific sulfur-containing compound is used as an additive.
  • These additives have an abrasion resistance effect and contribute to a reduction in the friction coefficient.
  • X ⁇ 1 >, X ⁇ 2 > shows an oxygen atom or a sulfur atom.
  • R 1 represents an organic group having 2 to 30 carbon atoms containing an oxygen atom or a sulfur atom.
  • n is an integer selected from 1 to 3.
  • a compound in which at least one of X 1 and X 2 is an oxygen atom is preferable.
  • R 4 represents an organic group having 4 to 24 carbon atoms
  • R 5 represents a divalent organic group having 1 to 6 carbon atoms
  • n is an integer selected from 1 to 3.
  • a hydrocarbon group having 4 to 24 carbon atoms is preferable, and an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group and the like are used, and an alkyl group having 8 to 16 carbon atoms is particularly preferable.
  • R 5 is preferably a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms.
  • methylene group ethylene group, 1,2-propylene group; 1,3-propylene group, various butylene groups, various pentylene groups, divalent aliphatic groups such as various hexylene groups, cyclohexane, methylcyclopentane, etc.
  • An alicyclic group having two bonding sites on the alicyclic hydrocarbon, various phenylene groups and the like can be mentioned.
  • the phosphorus-containing compound represented by the general formula (I) or (III) include hydrogen (hexylthioethyl) phosphate, hydrogen (octylthioethyl) phosphate, hydrogen ( Dodecylthioethyl) phosphate, hydrogendi (hexadecylthioethyl) phosphate, hydrogenmono (hexylthioethyl) phosphate, hydrogenmono (octylthioethyl) phosphate, hydrogenmono (dodecyl) Thioethyl) phosphate, hydrogen mono (hexadecylthioethyl) phosphate, and the like.
  • the method for producing the phosphorus-containing compound can be obtained, for example, by reacting alkylthioalkyl alcohol or alkylthioalkoxide with phosphorus oxychloride (POCl 3 ) in the absence of a catalyst or a base.
  • phosphorus oxychloride POCl 3
  • the zinc compound used for the preparation of the phosphorus-zinc-containing compound metal zinc, zinc oxide, organic zinc compound, zinc oxyacid salt, zinc halide, zinc complex and the like are preferable, specifically zinc, zinc oxide, Zinc hydroxide, zinc chloride, zinc carbonate, zinc carboxylate, zinc complex and the like can be mentioned.
  • the reaction between the phosphorus-containing compound and the zinc compound can be obtained by reacting in the absence of a catalyst or in the presence of a catalyst. In this reaction, it is preferable to use the phosphorus-containing compound and the zinc compound by reacting at a molar ratio of zinc atom to phosphorus atom (Zn / P) of 0.55 or more.
  • the reaction temperature is usually selected in the range of room temperature to 200 ° C., preferably 40 to 150 ° C.
  • the reaction product thus obtained is mainly composed of a zinc salt of a phosphorus-containing compound or the like, and the impurities are usually used after purification by a conventional method.
  • the sulfur-containing compound used in the present invention 1 has the general formula (II)
  • n is an integer selected from 1 to 5
  • R 2 and R 3 each independently contains an atom selected from an oxygen atom, a sulfur atom, and a nitrogen atom.
  • the 30 organic groups A 1 and A 2 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms.
  • R 6 and R 7 are each independently an organic group having 1 to 29 carbon atoms which may contain an atom selected from an oxygen atom, a sulfur atom and a nitrogen atom, A 3 and A 4 Each independently represents a divalent hydrocarbon group having 1 to 12 carbon atoms.
  • R 6 and R 7 may be linear, branched or cyclic, and preferably have 1 to 20 carbon atoms, more preferably 2 to 18 and particularly preferably 3 to 18 carbon atoms. .
  • a 3 and A 4 are preferably hydrocarbon groups having 1 to 8 carbon atoms.
  • Examples of the method for producing the sulfur-containing compound represented by the general formula (IV) include a method of oxidative coupling of a mercaptoalkanecarboxylic acid ester.
  • oxygen, hydrogen peroxide, dimethyl sulfoxide, or the like is used as the oxidizing agent.
  • sulfur-containing compound represented by the general formula (II) or (IV) include bis (methoxycarbonylmethyl) disulfide, bis (ethoxycarbonylmethyl) disulfide, bis (n-propoxycarbonylmethyl) disulfide, bis ( Isopropoxycarbonylmethyl) disulfide, bis (n-butoxycarbonylmethyl) disulfide, bis (n-octoxycarbonylmethyl) disulfide, bis (n-dodecyloxycarbonylmethyl) disulfide, bis (cyclopropoxycarbonylmethyl) disulfide, 1, 1-bis (1-methoxycarbonylethyl) disulfide, 1,1-bis (1-methoxycarbonyl-n-propyl) disulfide, 1,1-bis (1-methoxycarbonyl-n-butyl) disulfide 1,1-bis (1-methoxycarbonyl-n-hexyl) disulfide, 1,1-bis (1-methoxycarbon
  • the blending amount of the phosphorus-zinc-containing compound and the sulfur-containing compound is usually 0.05 to 5% by mass, preferably 0.1 to 4% by mass, based on the total amount of the composition.
  • the blending amount is 0.05% by mass or more, sufficient wear resistance is obtained, and when it is 5% by mass or less, there is no fear of corrosion.
  • the wear resistance is improved by these additives, so that a lubricating oil composition having sufficient properties can be obtained without using ZnDTP, and even when used in a low friction sliding material. A low coefficient of friction is obtained.
  • the blending amount of ZnDTP is small from the viewpoint of reducing the friction coefficient, which is usually 0.06% by mass or less in terms of phosphorus amount, and is not blended. Particularly preferred.
  • the lubricating oil composition of the present invention 1 may be blended with conventionally known additives as long as the effects of the present invention are not impaired.
  • metal detergents include improvers, pour point depressants, antioxidants, rust inhibitors, and the like.
  • metal detergents include alkaline earth metal sulfonates, salicinates, and finates. Among these, alkaline earth metal sulfonates and salicinates are preferable from the viewpoint of friction reduction.
  • Examples of the ashless dispersant include succinimides, boron-containing succinimides, benzylamines, boron-containing benzylamines, succinic esters, monovalent or divalent typified by fatty acids or succinic acid. Examples thereof include amides of carboxylic acids. Among these, succinimides containing no boron are preferable from the viewpoint of reducing friction. Examples of the friction reducing agent include ashless friction reducing agents such as fatty acid esters, aliphatic amines, and higher alcohols.
  • the viscosity index improver include so-called non-dispersion type viscosity index improvers such as various methacrylate esters or copolymers and hydrogenated products thereof, and various nitrogen compounds. Examples thereof include a so-called dispersed viscosity index improver obtained by copolymerizing a methacrylic acid ester.
  • non-dispersed or dispersed ethylene- ⁇ -olefin copolymers for example, propylene, 1-butene, 1-pentene etc.
  • hydrides thereof polyisobutylene and hydrogenated products thereof
  • styrene- Examples thereof include diene hydrogenated copolymers, styrene-maleic anhydride copolymers, and polyalkylstyrenes.
  • the molecular weight of these viscosity index improvers needs to be selected in consideration of shear stability.
  • the number average molecular weight of the viscosity index improver is, for example, 5000 to 1000000, preferably 100000 to 800000 for dispersed and non-dispersed polymethacrylates, 800 to 5000 for polyisobutylene or a hydride thereof, ethylene-
  • the ⁇ -olefin copolymer and its hydride are 800 to 300,000, preferably 10,000 to 200,000.
  • Such a viscosity index improver can be contained alone or in any combination of two or more kinds, but the content is usually about 0.1 to 40.0% by mass based on the total amount of the lubricating oil composition. is there.
  • the pour point depressant include polymethacrylate.
  • antioxidants include phenolic antioxidants and amine antioxidants.
  • phenolic antioxidants include 4,4′-methylenebis (2,6-di-t-butylphenol); 4,4′-bis (2,6-di-t-butylphenol); 4,4′- Bis (2-methyl-6-tert-butylphenol); 2,2′-methylenebis (4-ethyl-6-tert-butylphenol); 2,2′-methylenebis (4-methyl-6-tert-butylphenol); 4 4,4′-butylidenebis (3-methyl-6-tert-butylphenol); 4,4′-isopropylidenebis (2,6-di-tert-butylphenol); 2,2′-methylenebis (4-methyl-6- Nonylphenol); 2,2′-isobutylidenebis (4,6-dimethylphenol); 2,2′-methylenebis (4-methyl-6-cyclohexylphenol); 2,6-di t-butyl-4-methylphenol; 2,6-di
  • amine antioxidants include monooctyl diphenylamine; monoalkyl diphenylamines such as monononyl diphenylamine; 4,4′-dibutyldiphenylamine; 4,4′-dipentyldiphenylamine; 4,4′-dihexyldiphenylamine; 4,4′-diheptyldiphenylamine; 4,4′-dioctyldiphenylamine; dialkyldiphenylamines such as 4,4′-dinonyldiphenylamine; tetrabutyldiphenylamine; tetrahexyldiphenylamine; tetraoctyldiphenylamine; polyalkyldiphenylamine such as tetranonyldiphenylamine And naphthylamine type, specifically ⁇ -naphthylamine; phenyl- ⁇ -naphthylamine; and butylphenyl
  • dialkyldiphenylamine type and naphthylamine type are preferable.
  • the rust inhibitor include alkyl benzene sulfonate, dinonyl naphthalene sulfonate, alkenyl succinate, polyhydric alcohol ester and the like. The above is the description related to Invention 1.
  • the lubricating oil composition of the present invention 1 is applied to a sliding surface having a low friction sliding material, and can impart excellent low friction and wear resistance to the sliding mechanism (invention 2).
  • the sliding surface having the low friction sliding material preferably has a DLC material as a low friction sliding material on at least one side.
  • examples of the material of the other sliding surface include a DLC material, an iron-based material, and an aluminum alloy material. That is, both sliding surfaces are DLC material, one sliding surface is DLC material, the other sliding surface is iron-based material, one sliding surface is DLC material, and the other sliding surface is aluminum alloy material. A case can be illustrated.
  • the DLC material has a DLC film on the surface.
  • the DLC constituting the film is amorphous mainly composed of carbon elements, and the bonding form between carbons consists of both a diamond structure (SP 3 bond) and a graphite bond (SP 2 bond).
  • aC amorphous carbon
  • aC hydrogen amorphous carbon
  • some metal elements such as titanium (Ti) and molybdenum (Mo).
  • DLC is preferably DLC having a graphite crystal peak in the X-ray scattering spectrum.
  • a DLC having such a graphite crystal peak can be formed in a high-density plasma atmosphere by a cathode PIG (Penning Ionization Gauge) plasma CVD method.
  • PIG Powder Ionization Gauge
  • examples of the iron base material include carburized steel SCM420 and SCr420 (JIS).
  • the aluminum alloy material a hypoeutectic aluminum alloy or a hypereutectic aluminum alloy containing 4 to 20% by mass of silicon and 1.0 to 5.0% by mass of copper is preferably used.
  • AC2A, AC8A, ADC12, ADC14 (JIS), etc. can be mentioned.
  • the surface roughness of each of the DLC material and the iron base material, or the DLC material and the aluminum alloy material is preferably an arithmetic average roughness Ra of 0.1 ⁇ m or less from the viewpoint of sliding stability. is there.
  • the DLC material preferably has a surface hardness of Hv 1000 to 3500 in micro Vickers hardness (98 mN load) and a thickness of 0.3 to 2.0 ⁇ m.
  • the iron-based material preferably has a surface hardness of HRC45-60 in terms of Rockwell hardness (C scale). This case is effective because the durability of the film can be maintained even under sliding conditions under a high surface pressure of about 700 MPa as in a cam follower member.
  • the aluminum alloy material preferably has a surface hardness of Brinell hardness HB 80 to 130. When the surface hardness and thickness of the DLC material are within the above ranges, abrasion and peeling are suppressed. Further, when the surface hardness of the iron-based material is HRC45 or more, it is possible to suppress buckling and peeling under high surface pressure. On the other hand, if the surface hardness of the aluminum alloy material is within the above range, the wear of the aluminum alloy is suppressed.
  • the sliding part to which the lubricating oil composition of the present invention 1 is applied is not particularly limited as long as two metal surfaces are in contact with each other and at least one of them has a low friction sliding material.
  • the sliding part of an internal combustion engine can be mentioned preferably. In this case, it is effective because a low friction characteristic which is extremely excellent as compared with the conventional case is obtained and a fuel saving effect is exhibited.
  • the DLC member a disk-shaped shim or lifter crown surface coated with DLC on a steel material substrate is exemplified, and as the iron base member, low alloy chilled cast iron, carburized steel or tempered carbon steel, and The cam lobe using the material which concerns on these arbitrary combinations is mentioned.
  • the lubricating oil composition of the first invention can be preferably applied to the following sliding mechanism 1 (Invention 2).
  • a sliding mechanism 1 (Invention 2) of the present invention is a sliding mechanism in which the above lubricating oil composition is interposed between sliding surfaces of two sliding materials that slide on each other.
  • This is a sliding mechanism in which a DLC film containing 5 to 50 atom% hydrogen is formed on at least one sliding surface of the moving material.
  • the DLC film is more preferably a DLC film having a graphite crystal peak in an X-ray scattering spectrum.
  • FIG. 1 is a cross-sectional view schematically showing the structure of a sliding member having a DLC film of a sliding mechanism 1 according to an embodiment of the present invention 2 and FIG. It is sectional drawing which shows typically the structure of the sliding member which has a DLC film of the sliding mechanism which concerns on the form of. 1 and 2, 1 is a base material of a sliding material, 3 is a DLC film, and 4 is a graphite crystal.
  • An intermediate layer 2 as an adhesion layer is provided between the base material 1 of the sliding material and the DLC film 3.
  • an underlayer 21 may be provided as a second intermediate layer between the base material 1 and the intermediate layer 2. By providing the base layer 21, the adhesion between the base material 1 and the intermediate layer 2 can be further improved.
  • a DLC film having such a graphite crystal peak can be formed in a high-density plasma atmosphere by a cathode PIG (Penning Ionization Gauge) plasma CVD method.
  • the plasma generated in the cathode PIG is confined by being confined in a magnetic field formed by a coil, and the source gas is decomposed into active atoms, molecules, and ions with high efficiency.
  • high energy ions can be irradiated by applying a direct current pulse to the substrate while depositing a highly active source gas component. Thereby, a DLC film excellent in sliding characteristics can be efficiently formed.
  • the method described in Japanese Patent Application No. 2008-335718 is preferable.
  • FIG. 3 is a diagram showing an outline of an example of the cathode PIG plasma CVD apparatus.
  • 40 is a chamber
  • 41 is a substrate
  • 42 is a holder
  • 43 is a plasma source
  • 44 is an electrode
  • 45 is a coil
  • 46 is a cathode
  • 47 is a gas inlet
  • 48 is a gas outlet
  • 49 is a bias power source.
  • Reference numeral 50 denotes plasma formed in the chamber 40.
  • a DLC film can be formed as follows. First, the base material 41 is supported by the holder 42 and placed in the chamber 40. Next, Ar gas is injected from the gas inlet 47, and the plasma 50 is generated and stabilized using the plasma source 43, the electrode 44, and the coil 45.
  • the Ar gas decomposed in the plasma is attracted to the base material 41 by a bias power source 49 and surface etching is performed. Thereafter, a cathode 46 made of metal and a metal layer as an underlayer are formed using Ar gas. Furthermore, the raw material gas injected from the gas inlet 47 in a high-density plasma atmosphere is decomposed and reacted to generate graphite crystals in the DLC film. This is maintained until a DLC film having a predetermined thickness is obtained. At this time, the crystal diameter of the graphite crystal is controlled to be 15 to 100 nm. The crystal diameter is preferably 15 to 30 nm.
  • the cathode PIG plasma CVD apparatus it is possible to change the characteristics of the obtained DLC film by changing the plasma characteristics, gas types, etc.
  • the slidability and durability can be improved by optimizing the amount, hardness and surface roughness of the DLC film.
  • Confirmation of the presence of the graphite crystal and confirmation of the crystal diameter in the formed DLC film is preferably carried out using the following X-ray diffraction measurement.
  • an X-ray diffraction spectrum of a crystal material has a plurality of sharp diffraction peaks corresponding to individual lattice planes, and these are generally collated to determine a crystal structure.
  • FIG. 4 shows an X-ray diffraction spectrum measured for the DLC film containing graphite crystals under the following conditions. Measurement conditions X-ray source: radiation source, X-ray energy: 15 keV Incident slit width: 0.1 mm, Detector: Scintillation counter (a solar slit is placed in the previous stage), Measurement range of scattering angle 2 ⁇ : 5 to 100 ° Measurement step: 0.1 ° Integration time: 30 seconds / step The DLC film sample was peeled off from the substrate and filled into a glass capillary (capillary) for measurement.
  • X-ray source radiation source
  • X-ray energy 15 keV Incident slit width: 0.1 mm
  • Detector Scintillation counter (a solar slit is placed in the previous stage)
  • Measurement range of scattering angle 2 ⁇ 5 to 100 °
  • Measurement step 0.1 ° Integration time: 30 seconds / step
  • the DLC film sample was peeled off from the substrate and
  • FIG. 5 shows a differential spectrum for the same DLC film sample used in FIG.
  • peaks are selected in order from the largest peaks recognized in the differential spectrum, and if there are at least three peaks that coincide with the peak positions of the graphite crystals, the DLC film is a graphite crystal. It was prescribed that it contained.
  • This method is based on the Hanawalt method used in X-ray diffraction of a general crystal material, that is, a method of characterizing a diffraction pattern using three peaks having the highest intensity.
  • the crystal diameter of the graphite crystal can be estimated from the broadening of the diffraction peak as described above. Specifically, it can be obtained by subtracting the amorphous halo pattern from the X-ray scattering spectrum as the background, extracting the graphite crystal peak, and then applying the Scherrer equation shown in Equation 1.
  • D crystal diameter (nm) ⁇ : X-ray wavelength (nm)
  • ⁇ Half width of crystal peak (radian)
  • ⁇ Crystal peak position
  • the obtained DLC film has an amorphous structure mainly composed of carbon, and the bonding form between carbons consists of both a diamond structure (SP 3 structure) and a graphite structure (SP 2 structure). 10 to 35 atom%, preferably 20 to 30 atom% of hydrogen is contained in the film. If it is less than 10 atom%, the number of graphite crystals decreases to below the detection limit, and if it exceeds 35 atom%, the bonding between carbons decreases due to an increase in hydrogen termination, and the film hardness decreases and the wear resistance decreases.
  • SP 3 structure diamond structure
  • SP 2 structure graphite structure
  • an intermediate layer as an adhesion layer is provided as described above.
  • the intermediate layer for example, an intermediate layer composed of any one or more of a metal layer, a metal nitride layer, and a metal carbide layer selected from Ti, Cr, W, and Si is used.
  • a layer is desirable.
  • the total thickness of the intermediate layer is preferably 0.1 to 2.0 ⁇ m. That is, when the thickness is less than 0.1 ⁇ m, the function as the intermediate layer becomes insufficient. On the other hand, when the thickness exceeds 2.0 ⁇ m, the intermediate layer itself has a low hardness, which may reduce the impact resistance and adhesion.
  • the underlayer specifically, for example, a metal film selected from Ti, Cr, W, and Si can be given.
  • the sliding mechanism 1 according to the present invention 2 includes the above-described lubricating oil and sliding member. As described above, since both the lubricating oil and the sliding member have excellent low friction characteristics, a sufficiently low friction coefficient can be obtained.
  • the DLC film is formed on at least one of the sliding surfaces that slide on each other.
  • the sliding surface of the counterpart material is not particularly limited, and a DLC film may or may not be formed in the same manner.
  • examples of the counterpart material include the iron-based material and the aluminum alloy material described above. The above is the description of the sliding mechanism 1 (Invention 2).
  • the lubricating oil composition of the present invention 1 can be preferably applied to the following sliding mechanism 2 (invention 3).
  • DLC film also called “hard carbon film”
  • the present invention 3 has excellent low friction in a lubricating oil not containing ZnDTP or the like by adding W or Mo to the DLC film. It has been found that the characteristics can be exhibited. This is presumably because the additive in the lubricating oil is easily bonded to the atoms of W and Mo to form a tribo film, and excellent low friction characteristics are exhibited.
  • FIGS. 1 and 2 are cross-sectional views schematically showing a cross-sectional configuration of a DLC material according to another embodiment of the present invention 3.
  • FIG. The part names, the same numbers, and the functions in FIGS. 1 and 2 are as described in the sliding mechanism 2 (Invention 3).
  • This DLC film is amorphous mainly composed of carbon element, and contains 1 to 30 atom% of W or Mo.
  • the DLC film containing W or Mo is, for example, arc vapor deposition using a graphite raw material as a target, or arc vapor deposition using a W target or Mo target as a raw material while forming a DLC film on the surface of a target member by sputtering. It is produced by a method of flying a metal element by a sputtering method.
  • a plasma CVD method instead of arc deposition using a graphite raw material as a target or sputtering, a plasma CVD method in which a hydrocarbon gas such as acetylene or methane is plasma-decomposed and vapor-deposited is used.
  • a DLC film is formed on the surface, and then a metal element is produced by arc evaporation or sputtering using a W target or Mo target as a raw material.
  • the content of W or Mo is 1 atom% or more, the effect is recognized. However, when the content exceeds 30 atom%, the wear resistance is greatly lowered and the brittleness is lowered with a decrease in hardness. Therefore, it is preferably 1 to 30 atom%.
  • an intermediate layer as an adhesion layer is provided as described above.
  • the intermediate layer for example, an intermediate layer composed of any one or more of a metal layer, a metal nitride layer, and a metal carbide layer selected from Ti, Cr, W, and Si is used.
  • a layer is desirable.
  • the total thickness of the intermediate layer is preferably 0.1 to 2.0 ⁇ m. That is, when the thickness is less than 0.1 ⁇ m, the function as an intermediate layer is insufficient. On the other hand, when the thickness exceeds 2.0 ⁇ m, the intermediate layer itself has a low hardness, which may reduce the impact resistance and adhesion.
  • the underlayer specifically, for example, a metal film selected from Ti, Cr, W, and Si can be given.
  • the crystal diameter of the graphite crystal is desirably 15 to 100 nm.
  • the DLC film having a graphite crystal peak is as described in the second aspect of the invention.
  • a cathode PIG plasma CVD apparatus which is an example of a DLC film forming apparatus according to an embodiment of the present invention will be described with reference to FIG.
  • the part names, the same numbers and the functions in FIG. 3 are as described in the second aspect.
  • the process up to the formation of the metal layer as the underlayer using Ar gas is the same as in the case of the second aspect.
  • the graphite gas is further generated in the DLC film by decomposing and reacting the raw material gas injected from the gas introduction 47 in a high-density plasma atmosphere. This is maintained until a DLC film having a predetermined thickness is obtained. Then, while forming the DLC film in this way, arc vapor deposition and sputtering using W or Mo as a target are simultaneously performed.
  • the cathode PIG plasma CVD apparatus it is possible to change the characteristics of the obtained DLC film by changing the plasma characteristics, gas types, etc., and the amount and crystal diameter of the graphite crystals to be generated, the hardness of the DLC film.
  • the slidability and durability can be improved by optimizing the surface roughness and the like.
  • the confirmation of the presence of graphite crystals and the confirmation of the crystal diameter in the formed DLC film are performed using the X-ray diffraction measurement shown below.
  • FIG. 4 is an example in which an X-ray diffraction spectrum was actually measured for a DLC film containing graphite crystals.
  • the measurement conditions are as described in the second aspect.
  • the relationship between FIG. 4 and FIG. 5 is as described in the second aspect.
  • the relationship between the peak recognized in the differential spectrum and the method for characterizing the diffraction pattern is as described in the above-mentioned invention 2.
  • the crystal diameter of the graphite crystal can be estimated from the broadening of the diffraction peak as described above, and the relationship between FIG. 4 and FIG. 6 is as described in the invention 2.
  • the sliding mechanism 2 includes the above-described lubricating oil and a sliding member. As described above, since both the lubricating oil and the sliding member have excellent low friction characteristics, a sufficiently low friction coefficient can be obtained.
  • the DLC film is formed on at least one of the sliding surfaces that slide on each other.
  • the sliding surface of the counterpart material is not particularly limited, and a DLC film may or may not be formed in the same manner.
  • examples of the counterpart material include iron-based materials and aluminum alloy materials. As the iron-based material and the aluminum alloy material in Invention 3, those described in Invention 2 can be used.
  • the sliding part to which the sliding mechanism 2 of the present invention 3 is applied is not particularly limited as long as the two metal surfaces are in contact with each other and at least one of the surfaces has a low friction sliding material.
  • the sliding part of an internal combustion engine can be mentioned preferably. In this case, it is effective because a low friction characteristic which is extremely excellent as compared with the conventional case is obtained and a fuel saving effect is exhibited.
  • the DLC member a disk-shaped shim or lifter crown surface coated with DLC on a steel material substrate is exemplified, and as the iron base member, low alloy chilled cast iron, carburized steel or tempered carbon steel, and The cam lobe using the material which concerns on these arbitrary combinations is mentioned.
  • the friction coefficient in the sliding mechanism 1 was obtained under the conditions of a load of 400 N, an amplitude of 1.5 mm, a frequency of 50 Hz, and a temperature of 80 ° C. with an SCM420 cylinder ( ⁇ 15 mm ⁇ 22 mm) set on the top of the disk.
  • the components used in the preparation of the lubricating oil composition of Invention 1 and the comparative lubricating oil composition are as follows.
  • Lubricating base oil hydrocracked mineral oil (100 ° C. kinematic viscosity 4.47 mm 2 / s)
  • Sulfur-containing compound bis (n-octoxycarbonylmethyl) disulfide (sulfur content 15.8 mass)
  • Phosphorus-zinc-containing compound bis (octylthioester) zinc phosphate (phosphorus content 6.2 mass%, sulfur content 10.4 mass%)
  • Zinc dialkyldithiophosphate Zinc secondary alkyl-type dialkyldithiophosphate (phosphorus content 8.2% by mass)
  • Zinc dialkyldithiophosphate Zinc secondary alkyl-type dialkyldithiophosphate (phosphorus content 8.2% by mass)
  • Zinc dialkyldithiophosphate (2): Secondary alkyl-type zinc dialkyldithiophosphat
  • DLC-coated discs were used.
  • DLC DLC containing 20 atom% hydrogen (graphite crystal grain size: 20 nm)
  • DLC W 20 atom% hydrogen (tungsten added)
  • DLC graphite crystal grain size: 20 nm
  • the intermediate layer in the DLC coating was made of Ti for both DLC and DLC W, and the total thickness was 3.0 ⁇ m.
  • Example 4 and 5 A friction characteristic test was similarly performed by combining the following lubricating oil and sliding member, and a friction coefficient was obtained. The results are shown in Table 3.
  • Lubricating oil OIL1 Lubricating oil comprising the lubricating oil composition described in Example 1
  • OIL2 Lubricating oil comprising the lubricating oil composition described in Comparative Example 1
  • Sliding member (test piece) As a test piece, a disk coated with the following DLC film was used.
  • DLC1 DLC film with graphite crystal peak in X-ray scattering spectrum (graphite grain size: 20 nm), hydrogen content 25 atom%, DLC2 by cathode PIG plasma CVD method: Graphite crystal peak in X-ray scattering spectrum
  • the hydrogen-containing DLC film, the hydrogen content of 30 atom%, and the intermediate layer in the DLC coating by the high-frequency plasma CVD method consisted of Ti for both DLC 1 and 2, and the total thickness was 3.0 ⁇ m.
  • Table 3 shows the following.
  • the friction coefficient in the sliding mechanism 1 of the invention 2 is lowered (Examples 4 and 5).
  • a lubricating oil composed of a lubricating oil composition containing no sulfur-containing compound or phosphorus-zinc-containing compound used in the present invention 1 is used, the friction coefficient cannot be reduced (Comparative Examples 4 and 5).
  • the lubricating oil comprising the same lubricating oil composition of the present invention 1 is used, the DLC film having a graphite crystal peak has a better friction reducing effect than the DLC film having no graphite crystal peak ( Comparison between Examples 4 and 5).
  • Example 6 to 8 Comparative Examples 6 to 10
  • OIL 1 used in Example 1 was used, and in Comparative Examples 7 to 10, OIL 2 used in Comparative Example 1 was used.
  • a disk ( ⁇ 24 mm ⁇ 7.9 mm) coated with the DLC film shown in Table 4 was prepared, and a friction characteristic test of the sliding mechanism 2 shown below was performed to obtain a friction coefficient.
  • the results are shown in Table 5.
  • a friction coefficient in the sliding mechanism 2 was obtained under the conditions of a load of 400 N, an amplitude of 1.5 mm, a frequency of 50 Hz, and a temperature of 80 ° C. with an SCM420 cylinder ( ⁇ 15 mm ⁇ 22 mm) set on the top of the disk.
  • the intermediate layer in the DLC coating was composed of W in DLC1, and composed of Mo in DLC2, and the total thickness thereof was 3.0 ⁇ m.
  • the lubricating oil composition of the present invention 1 is applied to a sliding surface made of a low-friction sliding material such as a DLC material, and can impart excellent low-friction characteristics, particularly when applied to an internal combustion engine. A fuel saving effect can be imparted. Further, the sliding mechanisms 1 and 2 of the present inventions 2 and 3 in which such lubricating oil is interposed are excellent in low friction.

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  • Chemical Vapour Deposition (AREA)

Abstract

Cette invention concerne une composition lubrifiante, qui est obtenue par mélange d'un additif choisi parmi des composés contenant du phosphore et du zinc spécifiques et des composés contenant du soufre spécifiques, et qui présente un coefficient de frottement extrêmement bas quand elle est utilisée à titre de lubrifiant pour un matériau de glissement à bas frottement. Un mécanisme à glissement qui est excellent en termes de bas frottement et utilise la composition lubrifiante selon l'invention en combinaison avec un élément de glissement pourvu d'un film de revêtement à base d'un matériau de glissement à bas frottement spécifique sur sa surface de glissement est également décrit. Le mécanisme à glissement est pourvu d'un film de revêtement DLC contenant de 5 à 50 % en atomes d'hydrogène, ou le mécanisme à glissement contient de 1 à 30 % en atomes de tungstène (W) ou de molybdène (Mo).
PCT/JP2010/065747 2009-09-15 2010-09-13 Composition lubrifiante et mécanisme à glissement l'utilisant WO2011034026A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US13/395,801 US20120177915A1 (en) 2009-09-15 2010-09-13 Lubricant composition and sliding mechanism using the lubricant composition
CN2010800418421A CN102597191A (zh) 2009-09-15 2010-09-13 润滑油组合物、使用该润滑油组合物的滑动机构
EP10817139.8A EP2479247A4 (fr) 2009-09-15 2010-09-13 Composition lubrifiante et mécanisme à glissement l'utilisant

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JP2009-213647 2009-09-15
JP2009213647 2009-09-15
JP2010126367A JP2011084721A (ja) 2009-09-15 2010-06-01 摺動機構
JP2010-126368 2010-06-01
JP2010126368A JP2011084722A (ja) 2009-09-15 2010-06-01 潤滑油組成物、該潤滑油組成物を用いた摺動機構
JP2010-126367 2010-06-01

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EP (1) EP2479247A4 (fr)
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KR (1) KR20120080174A (fr)
CN (1) CN102597191A (fr)
WO (1) WO2011034026A1 (fr)

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EP2479247A4 (fr) 2013-06-26
US20120177915A1 (en) 2012-07-12
EP2479247A1 (fr) 2012-07-25
JP2011084722A (ja) 2011-04-28
KR20120080174A (ko) 2012-07-16
CN102597191A (zh) 2012-07-18
JP2011084721A (ja) 2011-04-28

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